Polysulfone compositions and derivatives thereof

ABSTRACT

The compositions disclosed herein comprise compounds of the formula: 
     
         DOOCArO-ArSO.sub.2 Ar&#39;QAr&#39;SO.sub.2 Ar-OArCOOD              (I) 
    
     and also derivatives and polymers therefrom or from the compound: 
     
         X-ArSO.sub.2 Ar&#39;QAr&#39;SO.sub.2 Ar-X 
    
     in which compounds D is hydrogen, halogen or a monovalent hydrocarbon radical, preferably of 1-20 carbon atoms; Q is either --O-- or --SO 2  --; Ar and Ar&#39; are divalent aromatic groups including a multiplicity of aromatic groups linked by O, SO 2 , hydrocarbon groups, etc.; and X is preferably Cl but may be other halogen atoms. In these compounds, the central core or residue --ArSO 2  Ar&#39;QAr&#39;SO 2  Ar-- may be represented by A. Various derivatives and polymers having the core A are prepared, such as diamides of the formula R 2  NOCArO-A-OArCONR 2  ; polyester polymers of the formula [--OROOCArO-A-OArCO--]; polyarylate polymers of the formula [--ArCOOArO-A-OArOOCArCOO--]; polycarbonate polymers of the formula [--OCOOArO-A-OArOOCO--]; phenolic resins, and many other derivatives. These compositions exhibit many desirable properties and have many uses including the improvement or upgrading of polyethylene terephthalate (PET) and polybutyleneterephthalate (PBT) resins when blended therewith.

This application is a continuation-in-part of application Ser. No.280,950 filed July 6, 1981, and now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to various polysulfone derivatives. Morespecifically it relates to monomeric and polymeric derivatives. Stillmore specifically it relates to such compositions which may be derivedfrom compounds having the formula X--ArSO₂ Ar'QAr'SO₂ AR--X wherein thevarious symbols are as defined herein.

2. State of the Prior Art

Sulfone monomers and polysulfone polymers having the structure --Ar--SO₂-- therein are known. However applicant is not aware of any prior artshowing the specific polysulfone structures described herein.

SUMMARY OF THE INVENTION

In accordance with the present invention, polysulfone compounds havebeen found which are useful for preparing a variety of derivativessuitable for numerous purposes. These polysulfones have the formula:

    DOOCArO--ArSO.sub.2 Ar'QAR'SO.sub.2 Ar--OArCOOD            (I)

wherein D represents hydrogen, halogen or a monovalent hydrocarbongroup, preferably of 1-20 carbon atoms; Ar and Ar' are divalent aromaticradicals including a multiplicity of aromatic groups linked by O, SO₂,divalent hydrocarbon groups, etc., and Q represents O or SO₂. Thesecompounds may be prepared by the reaction of a hydroxy aromaticcarboxylic ester with

    X--ArSO.sub.2 Ar'QAr'SO.sub.2 Ar--X

wherein X is preferably chlorine but may be other halogen atoms, and theother symbols are as defined above. Where D is to represent hydrogen,the ester groups are hydrolyzed to the acid groups. The acid may beconverted to the acid halide by reaction with thionyl halide, preferablySOCl₂. In these and various other compounds described below, the centralcore or residue --ArSO₂ Ar'QAr'SO₂ Ar-- may be represented by A.

In addition to saturated aliphatic, cycloaliphatic and alkylaryl estersthe esters of compound I may also include unsaturated esters, such asallyl esters, propargyl esters, vinylaryl esters, propargyl aryl esters,etc.

In the above Formula I where D is defined as hydrogen, halogen or ahydrocarbon group, the halogen may be Br, I, F but is preferably Cl, andthe hydrocarbon may be aliphatic, aromatic, cycloaliphatic andcombinations of such radicals, including those which have ethylenic oracetylenic unstaturation therein.

The hydrocarbon groups may have attached thereto any group that will notinterfere with the preparation and functions of the compounds of thisinvention as described herein. Preferably these groups are hydrocarbonor a multiplicity of hydrocarbon groups joined by ether, sulfide, esterand sulfonyl groups such as --O--, --S--, --COO--, --OOC--, --S(O)₂ --,etc.

Typical monovalent hydrocarbon groups suitable in the above formulasinclude: --CH₃, --C₂ H₅, --C₃ H₇, --C₄ H₉, --C₆ H₁₃, --C₁₀ H₂₁, --C₁₈H₃₇, --C₆ H₁₁, --C₅ H₉, --C₅ H₈ CH₃, --C₆ H₁₀ C₂ H₅, --CH₂ C₆ H₁₁, --CH₂CH₂ C₆ H₁₁, --C₆ H₅, --C₆ H₄ CH₃, --C₆ H₄ C₃ H₇, --C₆ H₃ (CH₃)₂, --C₆ H₅OCH₃, --C₆ H₄ OC₂ H₅, --C₆ H₄ SCH₃, --C₆ H₄ OOCCH₃, --C₆ H₄ SO₂ C₆ H₅,--C₆ H₄ SO₂ C₆ H₄ CH₃, --C₆ H₄ SO₂ C₆ H₅, --C₆ H₃ (CH₃)OC₃ H₇, --C₆ H₄OC₆ H₄ CH₃, --C₁₀ H₈, --C₁₀ H₇ CH₃, --C₁₀ H₇ C₂ H₅, --C₁₀ H₆ (CH₃)₂,--C₁₀ H₆ OCH₃, --C₁₀ H₆ OOCCH₃, --(C₆ H₄)₃ C₃ H₇, --(C₆ H₄)₃ OC₄ H₉,--(C₆ H₄)₃ OC₆ H₅, --C₆ H₄ (OCH₂ CH₂)₂ H, --C₆ H₄ (OCH₂ CH₂)₃ H, --(C₆H₄ O)₃ C₃ H₇, --CH₂ CH₂ OCH₂ CH₂)₂ H, --CH₂ CH₂ (OCH₂ CH₂)₃ OOCCH₃,--CH₂ CH₂ OC₆ H₅, --CH₂ CH₂ OOCCH₃, --CH₂ CH(CH₃)OOCC₆ H₅, --C₆ H₄ COOC₂H₅, --CH₂ COOC₆ H₅, --C₆ H₄ CH═CH₂, --C₆ H₃ (CH₃)CH═CH₂, --C₆ H₄C(CH₃)═CH₂, --C₆ H₄ C.tbd.CH, etc.

The divalent aromatic radicals Ar and Ar' are preferably hydrocarbon butcan contain additional groups which will not interfere with the variousreactions involved in the preparation and use of the products of thisinvention.

These are divalent benzenoid radicals advantageously selected from thegroup consisting of: ##STR1## and multiples thereof connected to eachother by Z, for example, ##STR2## wherein Z is an alkylene chain of 1-3carbon atoms, --CH═CH--, or; --O--, --S--, --SO₂ --, ##STR3## wherein R"is selected from the group consisting of alkyl and aryl groups of 1-20,preferably 1 to 7 carbon atoms. Ar is preferably: ##STR4## where Z is analkylene chain of 1-3 carbon atoms, ##STR5## --O--, --S--, --CH═CH--,--SO₂ --, and y is 1 to 3. Particularly preferred for Ar and Ar' is the##STR6## radical.

Typical compounds of the formula X--ArSO₂ Ar'QAr'SO₂ Ar--X which can beused in the preparation of the compositions of this invention includethe following:

Cl--C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ --Cl

Cl--C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ --Cl

Cl--C₆ H₃ (CH₃)SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₃ (CH₃)--Cl

Br--C₁₀ H₆ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₁₀ H₆ --Br

Cl--C₆ H₄ SO₂ C₆ H₃ (C₂ H₅)SO₂ C₆ H₃ (C₂ H₅)SO₂ C₆ H₄ --Cl

I--C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ --I

F--C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ --F

Cl--C₆ H₄ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ C₆ H₄ --Cl

Cl--C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ --Cl

Cl--C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ --Cl

Cl--C₆ H₄ CH₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ CH₂ C₆ H₄ --Cl

Cl--C₆ H₄ CH═CHC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ CH═CHC₆ H₄ --Cl

Br--C₆ H₄ SO₂ C₁₀ H₆ SO₂ C₁₀ H₆ SO₂ C₆ H₄ --Br

These may be prepared in accordance with the procedures described belowin Examples A and B.

The compounds of Formula I are easily prepared by the reaction ofX--ArSO₂ Ar'QAr'SO₂ Ar--X (1 mole) with 2 moles of CH₃ OOCC₆ H₄ OH(available commercially as Parasept) preferably in the presence of ananhydrous medium such as dimethyl sulfoxide or other aprotic solvent,and an alkali metal hydroxide, such as NaOH. Other esters may be used inwhich the methyl group is replaced by other hydrocarbon groups or inwhich the phenylene (--C₆ H₄ --) radical is replaced by other divalentaromatic radicals. Because of economics and availability, Parasept ispreferred. The methyl or other hydrocarbon group may be replaced to givethe corresponding acid, acid halide or other ester groups by standardmethods of hydrolysis, reaction with SOCl₂ or ester interchange,respectively.

Various types of polymers may be prepared from the compounds of FormulaI. For example, polyesters and polyamides may be prepared by reactionwith polyols and polyamines, and additional polymers may be prepared bystandard, well known free radical polymerization techniques when the Dof the formula contains an unsaturated group, such as vinyl, propargyl,etc.

In conducting polymerizations various solvents may be used with thepolysulfones of this invention. The particular solvent used will dependon the specific polysulfone used. In many cases, the solvent may be anaprotic organic compound having a dielectric constant between 35 and 45,preferably one which is water soluble. Representative aprotic compoundsare N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylmethoxyacetamide, N-methyl caprolactam, caprolactam,N,N-dimethylacetamide, N,N-diethylacetamide, dimethyl sulfoxide,N-mexthyl-α-pyrrolidone, tetramethylurea, hexamethylphosphoramide,tetramethylene sulfone, N,N,N',N'-tetramethyl-α-ethylmalonamide,N,N,N',N'-tetramethylglutaramide, N,N,N',N'-tetramethylsuccinamide,thiobis(N,N-dimethylacetamide), bis(N,N-dimethylcarbamylmethyl)ether,N,N,N',N'-tetramethylfuraramide, methylsuccinonitrile,N,N-dimethylcyanoacetamide, N,N-dimethyl-β-cyano-propionamide,N-formylpiperidine and butyrolactone, etc.

Of these solvents, dimethylacetamide is most preferred. Other preferredsolvents are dimethylformamide, N-methyl pyrrolidone, dimethylsulfoxide, butyrolactone and caprolactam.

In many cases, non-aprotic solvents can be used. For example, xylene,phenol, anisole, benzonitrile, acetophenone, methylphenylether ormixtures of these with each other, the aprotic solvents or withrelatively poor solvents such as benzene, toluene cyclohexane,cyclohexene, dioxane, butyl cellosolve and the like.

The concentration of the polysulfone in the solvent can be in the rangeof 1 to 80% by weight of polysulfone and solvent depending on thepolysulfone, the solvent and the temperature used. Preferably, theconcentration is between 10 and 60% by weight.

Polymerization products of the present invention have application in awide variety of physical shapes and forms, including use as films,molding compounds, coatings, etc. The unusual heat stability andresistance to deformation at elevated temperatures in the cured statemakes these compositions especially unique. When used as films or whenmade into molded products, these polymers, including laminated productsprepared therefrom, not only possess excellent physical properties atroom temperature, but they retain their strength and excellent responseto work-loading at elevated temperatures for long periods of time.

Moreover, solutions of the curable compositions herein described can becoated on electrical conductors such as copper, aluminum, etc. andthereafter, the coated conductor can be heated at elevated temperaturesto remove the solvent and to effect curing of the resinous composition.If desired, an additional overcoat may be applied to such insulatedconductors including the use of polymeric coatings such as polyamides,polyesters, silicones, polyvinylformal resins, epoxy resins, polyimides,polytetrafluoro-ethylene, etc.

They can also be used as binders for asbestos fibers, carbon fibers andother fibrous materials in making brake linings. In addition, moldingcompositions and molded articles may be formed from the polymericcompositions in this invention by incorporating such fillers asasbestos, glass fibers, talc, quartz, powder, wood flour, finely dividedcarbon, silica, into such compositions prior to molding. Shaped articlesare formed under heat, or under heat and pressure in accordance withpractices well known in the art. In addition, various heat-resistantpigments and dyes may be incorporated as well as various types ofinhibitors, depending on the application intended.

Various other compounds or derivatives of this invention may be preparedfrom compound I or from the starting dihalide compound X--A--X. Forexample, compound I may be reacted with an amine, NHR₂, to give thecompound:

    R.sub.2 NOCArO--A--OArCONR.sub.2                           (II)

wherein R represents hydrogen or a hydrocarbon radical, preferably of1-20 carbon atoms. When a diamine is used, a polymer is produced havinga plurality of repeating units of the structure:

    --NR--R'--NR(O)CArO--A--OArC(O)--                          (III)

wherein R' is a divalent aliphatic, cycloaliphatic or aromatichydrocarbon radical.

Polymeric polyesters may be prepared by reacting compound I withapproximately equimolar proportions of a polyol, HOR'OH, such asethylene glycol, etc. Here again, the R' may be aliphatic,cycloaliphatic or aromatic. The resultant polymers have a repeating unitstructure of the formula:

    --OR'O(O)CArO--A--OArC(O)--                                (IV)

Various unsaturated aromatic ether compounds may be prepared by thereaction of vinylaryl, allylaryl and acetylenicaryl hydroxy compoundswith X--A--X to give diethers having the formula KO--A--OK (V), whereinK represents an aromatic group having a terminal vinyl or acetyleneradical, such as

CH₂ ═CH--Ar--O--A--O--Ar--CH═CH₂

CH₂ ═CHCH₂ ArO--A--OArCH₂ CH═CH₂

CH.tbd.CCH₂ ArO--A--OArCH₂ C.tbd.CH

CH₂ ═C(CH₃)ArO--A--O--Ar--C(CH₃)═CH₂

Dihydroxy aromatic compounds may be reacted with approximately equimolarproportions of X--A--X, preferably with at least two moles of dihydroxycompound per mole of X--A--X to give derivatives of the formula:

    HOArO--A--OArOH                                            (VI)

These derivatives (VI) may be condensed with aldehydes such asformaldehyde to produce resins having the repeating unit formula:##STR7##

Derivatives VI may also be reacted with aromatic dicarboxyl dihalidessuch as terephthalic dichloride, to give polymers having the repeatingunit:

    --ArO--A--OArOOCArCOO--                                    (VIII)

or with phosgene, etc., to give polycarbonate polymers having therepeating unit:

    --ArO--A--OArOOCO--.                                       (IX)

Reaction of polyesters IV derived from aromatic polyols, such ashydroquinone, p,p'-dihydroxydiphenyl, bis-phenol-A, etc., may beenhanced in heat resistance by reaction with the dihydroxy compounds VIor by the direct preparation of polyesters of very good heat resistanceby the reaction of derivative I with the dihydroxy compound VI to givepolymers having the repeating unit:

    --OOCArO--A--OArCOOArO--A--OAr--.                          (X)

The reaction of X--A--X with HOArNH₂, such as HOC₆ H₄ NH₂ gives thediamine of the formula:

    NH.sub.2 ArO--A--OArNH.sub.2                               (XI)

which, when reacted with the dicarboxy compound I gives a polyamidepolymer having repeating units of the formula:

    --NHARO--A--OArNHOCArO--A--OArCO.sub.13                    (XII)

While the formulas of the preceding compounds of this invention havebeen given in full, it is possible in view of the generally symmetricalnature of these compounds to abbreviate these by the use of brackets toinclude the duplicated portions. For example, Formula I can also bewritten as:

    [DOOCArO--ArSO.sub.2 Ar'].sub.2 Q                          (I)

By reacting the X--A--X compounds with an acyl aromatic hydroxy compoundsuch as a p-acyl-aryl hydroxide, for example m- orp-hydroxy-acetophenone, m- or p-benzoyl-phenol, 3-, 4- or6-acetyl-naphthol-1,1-, 5- or 6-acetyl-naphthol-2,4-acetyl-4'-hydroxy-diphenyl, 3-acetyl-4'-hydroxy-diphenyl oxide, etc.Compounds of this invention are preferred having terminal acyl groups.For example, the reaction of p-hydroxy-acetophenone with the X--A--Xcompound produced below in Example A gives the product:

    [CH.sub.3 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                                 (XIIIa)

and with p-hydroxybenzophenone, the product is:

    [C.sub.6 H.sub.5 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                         (XIIIb)

With the X--A--X compound produced below in Example B, the products arerespectively:

    [CH.sub.3 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                          (XIIIc)

and

    [C.sub.6 H.sub.5 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                  (XIIId)

Also included within the scope of this invention are compounds in whichthe terminal aromatic groups have a second --COOD group such asAr(COOR)₂, Ar(COOH)₂ and Ar(COOX)₂. For example, in the preparationdescribed in Example I, the p-hydroxy phenyl benzoate may be replaced byan equivalent amount of 4-hydroxy dimethyl phthalate to give the product

    (CH.sub.3 OOC).sub.2 C.sub.6 H.sub.3 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.3 (COOCH.sub.3).sub.2

These may be converted to the tetraacids and the tetraacid halides bythe procedures described above.

This group of compounds may be represented by the formula:

    (DOOC).sub.2 ArO--A--OAr(COOD).sub.2                       (XIV)

In turn these tetrafunctional compounds, by using the techniquesdescribed above, may be converted to:

    tetraamides: (R.sub.2 NOC).sub.2 ArO--A--OAr(CONR.sub.2)   (XIVe) ##STR8## and unsaturated polymerizable derivatives:

    (CH.sub.2 ═CHOOC).sub.2 ArO--A--OAr(COOCH═CH.sub.2).sub.2 (XIVg)

and

    (CH.tbd.CCH.sub.2 OOC).sub.2 ArO--A--OAr(COOC.tbd.CH).sub.2 (XIVh)

The polymers of formula XIVf and those produced by free radicalpolymerization of XIVg and XIVh are tractable products and may be ofboth thermoplastic and thermosetting types useful as coating materialsto give solvent and heat resistant films.

The dicarboxylate groups of formula XIV wherein the members ofrespective pairs of carboxy groups are positioned ortho or peri to eachother may be converted to polyimide polymers by using one mole of adiamine R'(NH₂)₂ per mole of formula XIV, which has been first convertedto the tetraacid chloride compound by reaction with thionyl chloride.Completion of reaction and removal of by-products and solvent gives apolymer having the repeating unit structure:

    --OAr(CO).sub.2 N--R'--N(OC).sub.2 ArO--A--                (XV)

The R' in the diamine is preferably aromatic in which case R' may bedefined as Ar. Typical diamines of the NH₂ --Ar--NH₂ formula are thosehaving the Ar groups as defined above.

Examples of aromatic diamines which are suitable to provide the divalentAr radicals include 4,4'-diaminodiphenyl propane, 4,4'-diamino-diphenylmethane, benzidine, 3,3'-dichlorobenzidene, 4,4'-diamino-diphenylsulfide, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl sulfone,4,4'-diamino-diphenyl ether, 1,5-diamino naphthalene,4,4'-diaminodiphenyl diethylsilane, 4,4'-diamino-diphenyldiphenylsilane, 4,4'-diamino-diphenyl ethyl phosphine oxide,4,4'-diamino-diphenyl phenyl phosphine oxide, 4,4'-diamino-diphenylN-methyl amine, 4,4'-diamino-diphenyl N-phenyl amine and mixturesthereof, 3,3'-dimethyl-4,4'-diaminodiphenylmethane,3,3'-diethyl-4,4'-diaminodiphenylmethane,3,3'-dimethoxy-4,4'-diaminodiphenylmethane,3,3'-diethoxy-4,4'-diaminodiphenylmethane,3,3'-dichloro-4,4',4,4'-diaminodiphenylmethane,3,3'-dibromo-4,4'-diaminodiphenylmethane,3,3'-dicarboxy-4,4'-diaminophenylmethane,3,3'-dihydroxy-4,4'-diaminophenylmethane,3,3'-disulpho-4,4'-diaminodiphenylmethane,3,3'-dimethyl-4,4'-diaminodiphenylether,3,3'-diethyl-4,4'-diaminodiphenylether,3,3'-dimethoxy-4,4'-diaminodiphenylether, 3,3'-dibromo-4,4'-diaminodiphenylether, 3,3'-dicarboxy-4,4'-diaminodiphenylether,3,3'-dihydroxy-4,4' -diaminodiphenylether,3,3'-disulfo-4,4'-diaminodiphenylether,3,3'-dimethyl-4,4'-diaminodiphenylsulfide,3,3'-diethyl-4,4'-diaminodiphenylsulfide,3,3'-dimethoxy-4,4'-diaminodiphenylsulfide,3,3'-diethoxy-4,4'-diaminodiphenylsulfide,3,3'-dichloro-4,4'-diaminodiphenylsulfide,3,3'-dibromo-4,4'-diaminodiphenylsulfide,3,3'-dicarboxyl-4,4'-diaminodiphenylsulfide,3,3'-dihydroxy-4,4'-diaminodiphenylsulfide,3,3'-disulfo-4,4'-diaminodiphenylsulfide,3,3'-dimethyl-4,4'-diaminodiphenylsulfone,3,3'-diethoxy-4,4'-diaminodiphenylsulfone,3,3'-dichloro-4,4'-diaminodiphenylfulfone,3,3'-dicarboxy-4,4'-diaminodiphenylsulfone,3,3'-dihydroxy-4,4'-diaminodiphenylsulfone,3,3'-disulfo-4,4'-diaminodiphenylsulfone,3,3'-diethyl-4,4'-diaminodiphenylpropane,3,3'-dimethoxy-4,4'-diaminodiphenylpropane,3,3'-dichloro-4,4'-diaminodiphenylpropane,3,3'-dicarboxy-4,4'-diaminodiphenylpropane,3,3'-dihydroxy-4,4'-diaminodiphenylpropane,3,3'-disulfo-4,4'-diaminodiphenylpropane,3,3'-dimethyl-4,4'-diaminobenzophenone,3,3'-dimethoxy-4,4'-diaminobenzophenone,3,3'-dichloro-4,4'-diaminobenzophenone,3,3'-dibromo-4,4'-diaminobenzophenone,3,3'-dicarboxy-4,4'-diaminobenzophenone,3,3'-dihydroxy-4,4'-diaminobenzophenone,3,3'-disulphodiaminobenzophenone, 3,3'-diaminodiphenylmethane,3,3'-diaminodiphenylether, 3,3'-diaminodiphenylsulfide,3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylpropane,3,3'-diaminobenzophenone, 2,4-diaminotoluene, 2,6-diaminotoluene,1-isopropyl-2,4-phenylenediamine, diaminoanisole,2,4-diaminomonochlorobenzene, 4,4-diaminofluorobenzene,2,4-diaminobenzoic acid, 2,4-diaminophenol and2,4-diaminobenzenesulfonic acid and phenylene diamines. Preferreddiamines are 4,4'-oxydianiline, 4,4'-sulfonyldianiline, 4,4'-methylenedianiline, 4,4'-diaminobenzophenone, 4,4; diaminostilbene and thephenylene diamines, 2,4-diaminotoluene and all the meta and para isomersof H₂ NC₆ H₄ OC₆ H₄ OC₆ H₄ NH₂ .

SPECIFIC EMBODIMENT

The practice of this invention is illustrated by the following examples.These examples are given merely by way of illustration and are notintended to limit the scope of the invention in any way nor the mannerin which the invention can be practiced. Unless specifically indicatedotherwise, parts and percentages are given as parts and percentages byweight.

EXAMPLE A

Synthesis of 4,4'-bis(4-chlorobenzenesulfonyl)diphenylether

In a one liter round-bottom flask equipped with a stirrer, nitrogeninlet tube and reflux condenser, the top of which is connected to abubbler and caustic absorber, is placed 170.2 gm. (1 mole) of diphenylether, 422 gms. (2 moles) of 4-chlorobenzene sulfonyl chloride and 16gms. (0.1 mole) anhydrous ferric chloride. The mixture is heated at170°-175° C. for a period of six hours during which time the solutionthickens noticeably. The material is then allowed to cool to roomtemperature and recrystallized from approximately twice its volume ofacetone. The yield is 466 gms. (90%) of a product with a melting point(determined by DSC) of 164° C. The elemental analyses of C: 55.29%, S:12.27% and Cl: 13.58% are in good agreement with the theoretical valuesC: 55.38%; H: 3.03%; O: 15.38%; Cl: 13.65% and S: 12.31% (MW 520) for acompound of the formula (C₂₄ H₁₆ O₅ Cl₂ S₂), that is:

ClC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ Cl

The foregoing procedure is repeated a number of times using in place ofthe 4-chlorobenzene sulfonyl chloride equivalent amounts respectively of4-chloro-3-methylbenzene sulfonyl chloride; 4-bromobenzene sulfonylchloride; 4-chloro-naphthalene-1-sulfonyl chloride and 4'-chlorodiphenyloxide-4-sulfonyl chloride. The following compounds are obtainedrespectively:

Cl--C₆ H₃ (CH₃)SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₃ (CH₃)--Cl

Br--C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ --Br

Cl--C₁₀ H₆ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₁₀ H₆ --Cl

Cl--C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ --Cl

When the foregoing procedure is again repeated a number of times usingin place of the diphenyl oxide equivalent amounts respectively of3,3'-dimethyldiphenyl oxide, 1,1'-dinaphthylether and4,4'-bis(phenoxy)diphenylether, the following compounds are obtainedrespectively:

Cl--C₆ H₄ SO₂ C₆ H₃ (CH₃)OC₆ H₃ (CH₃)SO₂ C₆ H₄ --Cl

Cl--C₆ H₄ SO₂ C₁₀ H₆ OC₁₀ H₆ SO₂ C₆ H₄ --Cl

Cl--C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ OC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ --Cl

EXAMPLE B

Synthesis of 4,4'-bis(4-chlorobenzenesulfonyl)diphenyl sulfone

Substitution of 218.2 gms. (1 mole) of diphenyl sulfone, C₆ H₅ SO₂ C₆ H₅for the diphenyl oxide of Example I yields the corresponding compoundClC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ Cl, having elemental analyses of60.62% C and 16.69% S, which are in good agreement with the compound:

C₂₄ H₁₆ O₆ Cl₂ S₃ (MW 568)

The foregoing procedure is repeated a number of times using in place ofthe 4-chlorobenzene sulfonyl chloride equivalent amounts respectively of4-chloro-3-methylbenzene sulfonyl chloride; 4-bromobenzene sulfonylchloride; 4-chloro-naphthalene-1-sulfonyl chloride and4-chloro-diphenyloxide-4'-sulfonyl chloride. The following compounds areobtained respectively:

Cl--C₆ H₃ (CH₃)SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₃ (CH₃)--Cl

Br--C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ --Br

Cl--C₁₀ H₆ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₁₀ H₆ --Cl

Cl--C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ --Cl

When the foregoing procedure is again repeated a number of times usingin place of the diphenyl sulfone equivalent amounts respectively of3,3'-dimethyldiphenylsulfone; 1,1'-dinaphthylsulfone and4,4'-bis(phenoxy)diphenylsulfone. The following compounds are obtainedrespectively:

Cl--C₆ H₄ SO₂ C₆ H₃ (CH₃)SO₂ C₆ H₃ (CH₃)SO₂ C₆ H₄ --Cl

Cl--C₆ H₄ SO₂ C₁₀ H₆ SO₂ C₁₀ H₆ SO₂ C₆ H₄ --Cl

Cl--C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ --Cl

EXAMPLE Ia

Synthesis of Diesters of the Formula ROOCArO-A-OArCOOR

Into a one liter flask equipped with a stirrer, a Dean-Stark trap and anitrogen gas inlet tube is placed 214 gms. (1 mole) of para-hydroxyphenyl benzoate, HOC₆ H₄ COOC₆ H₅ and 40 gms. (1 mole) of sodiumhydroxide dissolved in 500 ml. of 95% ethyl alcohol. The mixture isheated gently to distill off the ethyl alcohol until a solid phasebegins to appear. Then 250 ml. of toluene and 250 ml. of dimethylsulfoxide is added and the mixture is heated to reflux under nitrogenuntil no more water is collected in the Dean-Stark trap. The toluene isthen distilled from the mixture and an additional 150 ml. of dimethylsulfoxide is added. To this solution is added 260 gms. (0.5 mole) of4,4'-bis(4-chlorobenzenesulfonyl)diphenylether and the mixture is heatedwith stirring under nitrogen for four hours at 160°-165° C. Then most ofthe dimethyl sulfoxide is recovered by distillation at 15 mm. Hgpressure in a rotary evaporator after which the residue is washed withhot water to extract sodium chloride. The crude product is dried in avacuum oven at 15 mm. pressure for 24 hours and shows a melting point of170°-173° C. A white sample recrystallized from alcohol-acetone solutionshows elemental analyses of C: 67.73%; H: 3.74% and S: 7.48% which arein good agreement with a compound having the formula C₅₀ H₃₄ O₁₁ S₂ anda molecular weight of 875, more specifically:

    H.sub.5 C.sub.6 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOC.sub.6 H.sub.5.                                       (Ia)

EXAMPLE Ib

Substitution of 152.15 g. of para-hydroxy methyl benzoate, HOC₆ H₄COOCH₃ (mole) for the equivalent amount of the phenyl ester of ExampleIa yields the corresponding ester (MW 751) (C₄₀ H₃₀ O₁₁ S₂):

    H.sub.3 COOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOC.sub.3 (Ib)

EXAMPLE Ic

Substitution of 284 g. (0.5 mole) of4,4'-bis(5-chlorobenzenesulfonyl)diphenyl sulfone for the4-4-bis(4-chlorosulfonyl)diphenyl ether of Example Ia yields thecorresponding ester (MW 923):

    H.sub.5 C.sub.6 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOC.sub.6 H.sub.5                                        (Ic)

EXAMPLE Id

Substitution of 248 g. (0.5 mole) of 4,4'-bis(4-chlorobenzenesulfonyl)diphenylsulfone for the 4,4-bis(4-chlorosulfonyl)ether ofExample Ib yields the corresponding ester (MW 799):

    H.sub.3 COOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOCH.sub.3                                               (Id)

Various other esters of Formula I are similarly prepared by usinghydroxy aryl esters of the formula HOArCOOR where R and Ar representother hydrocarbon and aromatic groups, and also by using other X--A--Xcompounds having different Ar and Ar' groups as described herein. Forexample, by using the appropriate hydroxy and ester compounds, thefollowing compounds are easily prepared:

    CH.sub.2 ═CHCH.sub.2 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 --COOCH.sub.2 CH═CH.sub.2                     (Ie)

    CH.sub.2 ═CHC.sub.6 H.sub.4 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 CH═CH.sub.2       (If)

    HC.tbd.CC.sub.6 H.sub.4 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 C.sub.6 H.sub.4 C.tbd.CH               (Ig)

Hydrolysis of the products of Examples 1a through Id, for example withaqueous NaOH solution, produces the respective diacids of the formulaHOOCArO--A--OAr--COOH, for example:

    HOOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOH    (Ih)

and

    HOOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOH (Ii)

Where other Ar and Ar' groups are present the diacid compounds willdiffer accordingly.

The free diacids may be easily converted by reaction with thionylhalides, such as thionyl chloride (SOCl₂) or with phosphorus halides(PCl₅ or PCl₃) to give the corresponding diacid halides of the formulaXOCAr--O--A--OArCOX. For example, reaction of compounds Ih and Ii withSOCl₂, under the usual conditions for such reactions, produces:

    ClOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COCl    (Ij)

and

    ClOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COCl (Ik)

EXAMPLE II

Preparation of Diamides of Compound I having the Formula R₂NOCAr--O--A--OArCONR₂

To a one-liter flask equipped with a stirrer, a reflux condenser and anitrogen atmosphere, with an ice water bath to control temperature,there is added 200 ml. of ether, 9.92 gms. (0.22 moles) of dimethylamine and 17.7 gms. (0.3 moles) of trimethyl amine. The temperature ismaintained at approximately 0° C. while a solution is slowly added whichcontains 63.5 gms. (0.1 mole) of the acid chloride Ij in ether. Stirringis continued for 30 minutes after the addition is completed. Theresultant solution is decanted from the precipitated trimethylaminehydrochloride and the precipitate washed with ether with the ether washbeing added to the product solution. The ether and excess trimethylamineand dimethylamine are evaporated from the product. Elemental analyses of64.88% C and 4.61% H check closely with the theoretical values for thecompound:

    (CH.sub.3).sub.2 NOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CON(CH.sub.3).sub.2                                       (IIa)

When the above procedure is repeated using an equivalent amount of theacid chloride Ik in place of the acid chloride Ij, there is obtained:

    (CH.sub.3).sub.2 NOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CON(CH.sub.3).sub.2                                       (IIb)

Repetition of the above procedure with various other amines of theformula R₂ NH and appropriate modifications of conditions are used toprepare:

    NH.sub.2 OCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CONH.sub.2 (IIc)

    NH.sub.2 OCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CONH.sub.2                                                (IId)

    C.sub.6 H.sub.5 NHOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CONHC.sub.6 H.sub.5                                       (IIe)

    C.sub.6 H.sub.11 NHOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CONHC.sub.6 H.sub.11                                      (IIf)

    (C.sub.2 H.sub.5).sub.2 NOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CON(C.sub.2 H.sub.5).sub.2                                (IIg)

These amide derivatives may also be made from the acids Ih and Ii andalso from the esters Ia-Id.

EXAMPLE III

Preparation of Polymeric Polyamides Having the Repeating Unit Formula

    --N(R)--R'--N(R)(O)CArO--A--OArC(O)--                      (III)

Into a one-liter flask equipped with a stirrer, a Dean-Stark trap and anitrogen gas inlet is placed 173.25 gms (0.25 mole) of the free acid Ih,27 gms (0.25 mole) of phenylene diamine, 200 ml. of dimethyl sulfoxideand 200 ml. of toluene. The mixture is refluxed under nitrogen until nomore water is collected in the Dean-Stark trap. Then the toluene isdistilled from the mixture and films laid from the resulting polymersolution. Evaporation of the solvent leaves films of good hardness andheat resistance and elemental analyses show values of 66.46% C and 3.78%H which is in good agreement with repeating units of the formula:

    --NHC.sub.6 H.sub.4 NHOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CO--(IIIa)

When the above procedure is repeated using acid Ii in place of Ih, thepolymer repeating units have the formula:

    --NHC.sub.6 H.sub.4 NHOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CO--                                                      (IIIb)

When ethylene diamine is used in equivalent amounts in place of thephenylene diamine, the respective polymer units have the formulas

    --NHCH.sub.2 CH.sub.2 NHOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CO--(IIIc)

and

    --NHCH.sub.2 CH.sub.2 NHOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CO--                                                      (IIId)

With diphenyldiamine, naphthalene diamine, 1,4 butylenediamine,cyclohexane-1,4-diamine, the respective polymer repeating units are:

--NHC₆ H₄ C₆ H₄ NHOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CO--

--NHC₆ H₄ C₆ H₄ NHOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄CO--

--NHC₁₀ H₆ NHOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CO--

--NHC₁₀ H₆ NHOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CO--

--NH(CH₂)₃ NHOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CO--

--NH(CH₂)₃ NHCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CO--

--NHC₆ H₁₀ NHOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CO--

--NHC₆ H₁₀ NHOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CO--

Replacement of the acids Ih and Ii in the foregoing procedures ofExample III with other acids of Formula I produce other polymericpolyamides of this invention.

Examples of aromatic diamines which are suitable for the preparation ofpolyamides according to the procedure of Example III include4,4'-diaminodiphenyl propane, 4,4'-diamino-diphenyl methane, benzidine,3,3'-dichlorobenzidene, 4,4'-diamino-diphenyl sulfide,3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl sulfone,4,4'-diamino-diphenyl ether, 1,4-diamino naphthalene,4,4'-diamino-diphenyl diethylsilane, 4,4'-diamino-diphenyldiphenylsilane, 4,4'-diamino-diphenyl ethyl phosphine oxide,4,4'-diamino-diphenyl phenyl phosphine 1,4-diamino naphthalene,4,4'-diamino-diphenyl diethylsilane, 4,4'-diamino-diphenyldiphenylsilane, 4,4'-diamino-diphenyl ethyl phosphine oxide,4,4'-diamino-diphenyl phenyl phosphine oxide, 4,4'-diamino-diphenylN-methyl amine, 4,4'-diaminodiphenyl N-phenyl amine and mixturesthereof, 3,3'-dimethyl-4,4'-diaminodiphenylmethane,3,3'-diethyl-4,4'-diaminodiphenylmethane,3,3'-dimethoxy-4,4'-diaminodiphenylmethane,3,3'-diethoxy-4,4'-diaminodiphenylmethane,3,3'-dichloro-4,4',4,4'-diaminodiphenylmethane,3,3'-dibromo-4,4'-diaminodiphenylmethane,3,3'-dicarboxy-4,4'-diaminophenylmethane,3,3'-dihydroxy-4,4'-diaminophenylmethane,3,3'-disulpho-4,4'-diaminodiphenylmethane,3,3'-dimethyl-4,4'diaminodiphenylether,3,3'-diethyl-4,4'-diaminodiphenylether,3,3'-dimethoxy-4,4'-diaminodiphenylether,3,3'-disulfo-4,4'-diaminodiphenylether,3,3'-dimethyl-4,4'-diaminodiphenylsulfide,3,3'-diethyl-4,4'-diaminodiphenylsulfide,3,3'-diemthoxy-4,4'-diaminodiphenylsulfide,3,3'-diethoxy-4,4'-diaminodiphenylsulfide,3,3'-dichloro-4,4'-diaminodiphenylsulfide, 3,3'-dibromo-4,4'-diaminodiphenylsulfide,3,3'-dicarboxyl-4,4'-diaminodiphenylsulfide,3,3'-dihydroxy-4,4'-diaminodiphenylsulfide,3,3'-disulfo-4,4'-diaminodiphenylsulfide,3,3'-dimethyl-4,4'-diaminodiphenylsulfone,3,3'-diethoxy-4,4'-diaminodiphenylsulfone,3,3'-dichloro-4,4'-diaminodiphenylsulfone,3,3'-dicarboxy-4,4'-diaminodiphenylsulfone,3,3'-dihydroxy-4,4'-diaminodiphenylsulfone,3,3'-disulfo-4,4'-diaminodiphenylsulfone,3,3'-diethyl-4,4'-diaminodiphenylpropane,3,3'-dimethoxy-4,4'-diaminodiphenylpropane,3,3'-dichloro-4,4'-diaminodiphenylpropane,3,3'-dicarobxy-4,4'-diaminodiphenylpropane,3,3'-dihydroxy-4,4'-diaminodiphenylpropane,3,3'-disulfo-4,4'-diaminodiphenylpropane,3,3'-dimethyl-4,4'-diaminobenzophenone,3,3'-dimethoxy-4,4'-diaminobenzophenone,3,3'-dichloro-4,4'-diaminobenzophenone,3,3'-dibromo-4,4'-diaminobenzophenone,3,3'-dicarboxy-4,4'-diaminobenzophenone,3,3'-dihydroxy-4,4'-diaminobenzophenone,3,3'-disulphodiaminobenzophenone, 3,3'-diaminodiphenylmethane,3,3'-diaminodiphenylether, 3,3'-diaminodiphenylsulfide,3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylpropane,3,3'-diaminobenzophenone, 2,4-diaminotoluene, 2,6-diaminotoluene,1-isopropyl-2,4-phenylenediamine, 2,4-diaminoanisole,2,4-diaminomonochlorobenzene, 2,4-diaminofluorobenzene,2,4-diaminobenzoic acid, 2,4-diaminophenol and2,4-diaminobenzenesulfonic acid, and phenylene diamines. Preferreddiamines are 4,4'-oxydianiline, 4,4'-sulfonyldianiline, 4,4'-methylenedianiline, 4,4'-diaminobenzophenone, 4,4'-diaminostilbene and thephenylene diamines, 2,4-diaminotoluene and all the meta and para isomersof H₂ NC₆ H₄ OC₆ H₄ OC₆ H₄ NH₂.

Aliphatic and cycloaliphatic diamines which are also suitable include:ethylene diamine, propylene diamine, 1,4-butylene diamine, 1,3-propylenediamine, 2,3-butylene diamine, 1,4-amylene diamine, 2,3-amylene diamine,pentamethylene diamine, hexamethylene diamine, NH₂ (CH₂ CHRNH)_(X) H,wherein X may have a value of 2-20 and R is as defined above, preferablyhydrogen, cyclohexane-1,4-diamine, cycloheptane-1,4-diamine,cyclohexane-1,2-diamine, 1,4-bis(aminomethyl)cyclohexane,1,2-bis(aminomethyl)cyclohexane, etc.

EXAMPLE IV

Polyesters Having the Repeating Unit Formula

    --OR'O(O)CArO--A--OArC(O)--                                (IV)

The procedure of Example III is repeated using 1h and an equivalentamount of ethylene glycol in place of the phenyl diamine. A polyesterpolymer is obtained having a repeating unit structure having theformula:

    --OCH.sub.2 CH.sub.2 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--(IVa)

When the procedure is repeated using equivalent amounts respectively ofpropylene glycol, tetramethylene glycol, HO(CH₂ CH₂ O)₄ H, hydroquinone,cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol, polyesters areobtained having the following repeating unit structures respectively:

    --OCH.sub.2 CH(CH.sub.3)OOCC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--(IVb)

    --O(CH.sub.2).sub.3 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--(IVc)

    --O(CH.sub.2 CH.sub.2 O).sub.4 OCC.sub.6 H.sub.4 OC.sub.5 H.sub.4 SO.sub.2 C.sub.4 H.sub.3 OC.sub.6 H.sub.4 SO.sub.2 C.sub.5 H.sub.4 OC.sub.6 H.sub.4 C(O)--                                                    (IVd)

    --OC.sub.6 H.sub.4 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--(IVe)

    --OC.sub.6 H.sub.10 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--(IVf)

    --OCH.sub.2 C.sub.6 H.sub.10 CH.sub.2 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--(IVg)

When the above procedures of Example IV are repeated using Ii in placeof Ih, the following repeating unit structures are obtainedrespectively:

    --OCH.sub.2 CH(CH.sub.3)OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--                                            (IVh)

    --O(CH.sub.2).sub.4 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.6 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--                                                    (IVi)

    --O(CH.sub.2 CH.sub.2 O).sub.4 OCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--                                            (IVj)

    --OC.sub.6 H.sub.4 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--                                                    (IVk)

    --OC.sub.6 H.sub.10 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--                                                    (IVl)

    --OCH.sub.2 C.sub.6 H.sub.10 CH.sub.2 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)--                                   (IVm)

Aliphatic, aromatic and cycloaliphatic glycols which are also suitableinclude: ethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol,1,3-propylene glycol, 2,3-butylene glycol, 1,4-amylene glycol,2,3-amylene glycol, pentamethylene glycol, hexamethylene glycol, HO(CH₂CHRO)_(X) H, wherein X may have a value of 2-20 and R is as definedabove, preferably hydrogen, cyclohexane-1,4-diol, cycloheptane-1,4-diol,cyclohexane-1,2-diol, cyclohexane-1,4-dimethanol,cyclohexane-1,2-dimethanol, hydroquinone, resorcinol,p,p'-dihydroxydiphenyl, 1,4-dihydroxy-naphthalene, bis-phenol-A,dimethylolbenzene, dimethylolnaphthalene, dimethyloldiphenyl, etc.

In addition to replacing the glycols in the foregoing procedures ofExample IV, the replacement of acids Ih and Ii with other acids ofFormula I produce the corresponding polyester polymers of thisinvention.

EXAMPLE V

Preparation of Unsaturated Aromatic Ether Compounds Having the Formula

    KO--A--OK (wherein K represents an aromatic group having a terminal vinyl or acetylene radical)                                     (V)

The procedure of Example I is repeated using 120 gms. (1 mole) ofpara-hydroxy styrene in place of the para-hydroxy phenyl benzoate. Theproduct is recrystallized from alcohol-acetone solution and elementalanalyses of 69.89% C and 4.35% H show close agreement with the valuesof:

    CH.sub.2 ═CHC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH═CH.sub.2 (Va)

Repetition of this procedure using equivalent amounts respectively ofp-allyl phenol, p-propargyl phenol, 4-vinyl-1-naphthol and4'-vinyl-4-hydroxydiphenyl produce the following compounds:

    CH.sub.2 ═CHCH.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 CH═CH.sub.2                                  (Vb)

    CH.tbd.CCH.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.tbd.CH                                                  (Vc)

    CH.sub.2 ═CHC.sub.10 H.sub.6 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.10 H.sub.6 CH═CH.sub.2                                           (Vd)

    CH.sub.2 ═CHC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 CH═CH.sub.2                           (Ve)

Repetition of the above procedures using an equivalent amount of4,4'-bis(4-chlorosulfonyl)diphenylsulfone in place of the correspondingdiphenyl ether produces the following compounds:

    CH.sub.2 ═CHC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH═CH.sub.2                                           (Vf)

    CH.sub.2 ═CHCH.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 CH═CH.sub.2                                  (Vg)

    CH.tbd.CCH.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.tbd.CH                                         (Vh)

    CH.sub.2 ═CHC.sub.10 H.sub.6 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.10 H.sub.6 CH═CH.sub.2                                           (Vi)

    CH.sub.2 ═CHC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 CH═CH.sub.2                   (Vj)

The compounds of Example V having two terminal vinyl (CH₂ ═CH--) oracetylene (CH.tbd.C--) groups are polymerized to tough, infusiblepolymers using techniques known in the art for effecting additionpolymerization, such as with free radical-generating catalysts. Forexample, 5 g of compound Va is dissolved in 20 gms. of dimethylacetamideand 0.05 gms. of benzoyl peroxide is added. The solution is maintainedat 95°-105° C. for 3 hours. An insoluble, infusible polymer is obtained.Similar results are obtained when a portion of the Va compound isreplaced with a vinyl or vinylidene comonomer as follows:

a. 80% Va plus 20% styrene

b. 90% Va plus 10% acrylonitrile

c. 90% Va plus 10% methyl methacrylate

d. 50% Va plus 50% styrene

Similar results are also obtained when Va is replaced with correspondingamounts of compounds Vb through Vj respectively in each of the foregoingpolymerizations.

EXAMPLE VI

Preparation of Aromatic Ether Compounds Having A Terminal AromaticHydroxy Group of the Formula HOArO--A--OArOH

The procedure of Example Ia is repeated except that in place of thep-hydroxy phenyl benzoate there is used 110.11 gms. (1 mole) ofhydroquinone, and the 4,4'-bis(4-chlorosulfonyl)diphenylether is addedgradually over a period of one hour as a solution in the 150 mls ofdimethyl sulfoxide which is to be added after removal of the toluene.The product is recrystallized from alcohol-acetone solution and thevalues from elemental analyses 64.51% C and 4.09% H are in goodagreement for the compound:

    HOC.sub.6 H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 OH                                       (VIa)

By substituting equivalent amounts respectively of1,4-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bisphenol-A anddiphenylol-methane the following compounds are prepared:

    HOC.sub.10 H.sub.6 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.5 OC.sub.10 H.sub.6 OH     (VIb)

    HOC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 OH                                                        (VIc)

    HOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 OH     (VId)

    HOC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 OH                               (VIe)

When 4,4'-bis(4-chlorosulfonyl)diphenylsulfone is used in place of thecorresponding diphenyl ether in the five above procedures, the followingcompounds are prepared:

    HOC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.5 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 OH (VIf)

    HOC.sub.10 H.sub.6 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.10 H.sub.6 OH (VIg))

    HOC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 OH                                                (VIh)

    HOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 OH     (VIi)

    HOC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 OH                       (VIj)

EXAMPLE VII

Aldehyde Condensation Polymers Having the Repeating Unit Formula

    --CHR--Ar"(OH)O--A--OAr"(OH)--(wherein Ar" is a trivalent aromatic radical) (VII)

Into a one-liter flask equipped with a stirrer, condenser and a nitrogengas inlet tube is placed 400 ml of dimethyl sulfoxide and 166.5 gms(0.25 mole) of [HOC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ ]₂ O (VIa) and 0.4 gm oftriethylamine. In a separate flask there is placed 15 gms (equivalent to0.5 mole CH₂ O) of paraformaldehyde. A stream of nitrogen is fed intothis flask and through a tube into the first flask below the surface ofthe solution therein. The solution in the first flask is stirred andmaintained at 90° C. while a bunsen burner is applied to the secondflask containing the paraformaldehyde. As the paraformaldehyde issublimed it is carried by the stream of nitrogen into the solution inthe first flask. After the transfer of the paraformaldehyde (orformaldehyde) has been completed, the temperature of the solution ismaintained for another 4 hours. Most of the dimethyl sulfoxide isremoved by distillation at 15 mm. Hg pressure in a rotary evaporator.The product is dried in a vacuum oven at 15 mm. pressure for 24 hours.Then the product is pulverized and placed in a compression mold andmolded at 250° C. and 2500 psi to give a tough, insoluble,heat-resistant product.

Similar results are obtained with the dihydroxy compounds of VI b, c, d,e, f, g, h, i and j.

EXAMPLE VIII

Condensation Products Having the Formula

    --OCArCOOArO--A--OArO--                                    (VIII)

The procedure of Example VII is repeated except that the addition offormaldehyde (paraformaldehyde) is omitted. Instead there is addedgradually 48 gms. (0.25 mole) of terephthalyl dichloride and thetriethylamine is replaced with powdered NaOH to react with the HCl givenoff by the reaction. The precipitated sodium chloride is removed bydecantation or filtration. The recovered product gives a tough polymericfilm in which the polymer has the repeating unit structure:

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--(VIIIa)

Elemental analyses give values of 66.25% C and 3.47% H which checkclosely with the theoretical values for the above formula.

The foregoing procedure is repeated a number of times using respectivelythe other aromatic hydroxy-terminated compounds of above Example VI,namely compounds VIb through VIj. Polymers are obtained having thefollowing repeating unit structures respectively:

    --OCC.sub.6 H.sub.4 COOC.sub.10 H.sub.6 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.10 H.sub.6 O--                             (VIIIb)

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 C.sub.6 H.sub.4 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 O--              (VIIIc)

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 O--(VIIId)

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 CHC.sub.6 H.sub.4 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 O--     (VIIIe)

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--                      (VIIIf)

    --OCC.sub.6 H.sub.4 COOC.sub.10 H.sub.6 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.10 H.sub.6 O--                     (VIIIg)

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 C.sub.6 H.sub.4 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 O--      (VIIIh)

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 O--(VIIIi)

    --OCC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 O--

     C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 O--(VIIIj)

Similar polymers are also obtained when the terephthalyl dichloride isreplaced with equivalent amounts respectively of 1,4-phthalyldichloride; 2,3-naphthalene dicarboxydichloride, 1,4-naphthalenedicarboxydichloride, peri-naphthalene dicarboxydichloride, 3,4-diphenyldicarboxydichloride, 4,4'-diphenyl dicarboxychloride, 4,4'-diphenyloxidedicarboxyldichloride, 4,4'-diphenyl methane dicarboxydichloride,4,4'-diphenylsulfide dicarboxydichloride and 3,3'-diphenylsulfonedicarboxydichloride.

EXAMPLE IX

Condensation Products of Phenylol-Terminated Polysulfone Polymers withPhosgene to Give Polymers Having the Repeating Unit Formula

    --OCOArO--A--OArO--                                        (IX)

The procedure of Example VIII is repeated except that the terephthalyldichloride is omitted and instead 25 gms. (0.25 mole) of phosgene is fedin gradually through a tube as the formaldehyde is fed in a nitrogenstream as described in Example VII. The resultant polymeric film has therepeating unit structure:

    --OCOC.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--     (IXa)

Elemental analyses give values of 64.10% C and 3.39% H which correspondclosely with the theoretical values for the preceding formula.

The foregoing procedure is repeated a number of times using respectivelythe other aromatic hydroxy-terminated compounds of above Example VInamely compounds VIb through VIj. Polymers are obtained having thefollowing repeating unit structures respectively:

    --OCOC.sub.10 H.sub.6 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.10 H.sub.6 O--    (IXb)

    --OCOC.sub.6 H.sub.4 C.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.3 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--(IXc)

    --OCOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 --C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 O--    (IXd)

    --OCOC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 O--                              (IXe)

    --OCOC.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--(IXf)

    --OCOC.sub.10 H.sub.6 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.10 H.sub.6 O--(IXg)

    --OCOC.sub.6 H.sub.4 C.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 O--                                       (IXh)

    --OCOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 O--                     (IXi)

    --OCOC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.4 O--                      (IXj)

Similar results in producing polycarbonate polymers are also obtainedwhen the phosgene is replaced with equivalent amounts respectively ofdiaryl carbonates, namely diphenyl carbonate, ditolyl carbonate,dinaphthyl carbonate, di(diphenyl)carbonate, etc., preferably in thepresence of zinc acetate dihydrate (0.25%) and at a temperature of190°-195° C. The phenol or other by-product is removed by distillation.

EXAMPLE X

Reaction of Compounds I with Dihydroxy Compounds VI to PreparePolyesters Having the Repeating Unit Formula

    --(O)CArO--A--OArC(O)OArO--A--OArO--                       (X)

Compounds I, namely [DOOCArOArSO₂ Ar']₂ Q, in either acid, ester or acidhalide form may be reacted with compound VI, namely [HOArOArSO₂ Ar']₂ Qto replace the D group with polyester linkages between said compounds toprepare polymers having repeating units of the formula:

    --OCArO--ArSO.sub.2 Ar'QAr'SO.sub.2 ArOArCOOArOArSO.sub.2 Ar'QAr'

     SO.sub.2 ArOArO--                                         (X)

Thus 150.0 gms. (0.2 mole) of

    [CH.sub.3 OOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                                 (Ib)

and 142.8 (0.2 mole of

    [HOC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                                  (VIf)

are added to a one liter flask equipped with stirrer, nitrogen inlettube and Dean-Stark trap, containing 300 ml. of dimethyl sulfoxide and7.5 gms. of zinc acetate dihydrate. This mixture is heated gradually upto 190° C. and maintained at 190°-195° C. for two hours during whichtime almost the theoretical amount of methanol is collected. The polymerproduct is recovered by removing most of the dimethyl sulfoxide bydistillation at 15 mm Hg pressure in a rotary evaporator. A filmobtained from the viscous concentration of the polymer is dried in avacuum oven at 15 mm pressure for 24 hours. The polymer film is toughand heat-resistant. Elemental analyses give values of 63.33% C and 3.39%H which values check closely with the theoretical values for the polymerhaving a repeating unit structure of the formula:

    --OCC.sub.6 H.sub.4 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 COOC.sub.6 H.sub.4 OC.sub.6 H.sub.4

     SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--                                      (Xa)

The above procedure is repeated a number of times using equivalentamounts respectively of the following combinations:

(b) Ic and VIa

(c) Id and VIc

(d) Ie and VId

(e) If and VIe

(f) Ig and VIg

(g) Ii and VIh

Similar polymers fitting the above repeating unit X are obtained in eachcase. Similar polymers are obtained also when the I compounds arereacted in the acid and acid chloride forms with appropriatemodifications made in the reaction conditions.

EXAMPLE XI

Preparation of Diamines Having the Formula

    NR.sub.2 ArO--A--OArNR.sub.2                               (XI)

Into a 500 ml flask equipped with a stirrer, Dean-Stark trap, andnitrogen inlet tube is placed 66.1 gms. (0.606 moles) ofpara-aminophenol, and 24 gms. (0.6 mole) of sodium hydroxide dissolvedin 25 ml of water. Approximately 100 ml of toluene and 100 ml ofdimethylsulfoxide is then added. This mixture is heated to reflux undernitrogen and the water removed by the Dean-Stark trap. When no morewater is collected in the trap, toluene is distilled from the mixtureand an additional 100 ml of dimethylsulfoxide is added. To this solutionis added 156.6 gms. (0.30 mole) of4,4'-bis(4-chlorobenzenesulfonyl)diphenyl ether prepared according toExample A. This mixture is stirred under nitrogen while the temperatureis maintained for one hour and 25 minutes at 160° C. and then cooled toroom temperature. The resulting solution is diluted with 2.5 liters ofwater and made basic (pH approximately 8.0) with sodium hydroxide.Precipitation of the crude product is effected upon the addition of thesodium hydroxide. The precipitate is collected, washed with water andredissolved in 3 liters of dilute hydrochloric acid. This solution isslowly neutralized with sodium hydroxide to reprecipitate the product.After colllecting the product on a Buchner funnel, it is washed againwith cold water and dried in a vacuum to yield 131 gms. (65%) of acreamed colored product having a DSC melting point of 265° C. Elementalanalyses of 65.4% C and 4.19% H check closely with the values for theformula:

    H.sub.2 NC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 NH.sub.2 (XIa)

Replacement of the 4,4'-bis(4-chlorobenzenesulfonyl)diphenyl ether withequivalent amounts respectively of:

(b) [Cl--C₆ H₃ (CH₃)SO₂ C₆ H₄ ]₂ O

(c) [Cl--C₁₀ H₆ SO₂ C₆ H₄ ]₂ O

(d) [Cl--C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ ]₂ O

(e) [Cl--C₆ H₄ SO₂ C₆ H₄ ]₂ SO₂

(f) [Cl--C₁₀ H₆ SO₂ C₆ H₄ ]₂ SO₂

(g) [Cl--C₆ H₄ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ ]₂ SO₂

produce the following compounds respectively:

    [H.sub.2 NC.sub.6 H.sub.4 OC.sub.6 H.sub.3 (CH.sub.3)SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                         (XIb)

    [H.sub.2 NC.sub.6 H.sub.4 OC.sub.6 H.sub.3 (CH.sub.3)SO.sub.2 C.sub.6 H.sub.4 ]O                                                (XIc)

    [H.sub.2 NC.sub.6 H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                 (XId)

    [H.sub.2 NC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                                  (XIe)

    [H.sub.2 NC.sub.6 H.sub.4 OC.sub.10 H.sub.6 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                          (XIf)

    [H.sub.2 NC.sub.6 H.sub.4 OC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                 (XIg)

When in the procedure for XIa the p-aminophenol is replaced with anequivalent amount respectively of 1-aminonaphthol-4, 4-NH₂-4'-hydroxydiphenyl and 4-NH₂ -4'-hydroxydiphenyl oxide, the followingproducts are prepared respectively:

    [H.sub.2 NC.sub.10 H.sub.6 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                                 (XIh)

    [H.sub.2 NC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                         (XIi)

    [H.sub.2 NC.sub.6 H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                 (XIj)

EXAMPLE XII

Condensation of Dicarboxy Compound I with Diamine Compound XI to ProducePolyamides Having Repeating Units of the Formula

    --N(R)ArO--A--OArN(R)(O)CArO--A--OArC(O)--                 (XII)

Into a one liter flask equipped with a stirrer, condenser and a nitrogengas inlet tube is placed 200 ml. of dimethyl sulfoxide, 177.5 gms. (0.25mole) of [NH₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ ]₂ SO₂ (XIe) and 30 gms. (0.3 mole)of triethyl amine. Under a nitrogen atmosphere and with stirring, asolution is gradually added comprising 200 ml. of dimethyl sulfoxidecontaining 201.75 gms. (0.25 mole) of [ClOCC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ ]₂ SO₂(Ik). After completion of the addition, the temperature is raised to andmaintained at 90° C. for 2 hours. Then the solution is extracted withtwo 200 ml. portions of hot water to remove triethylamine hydrochlorideand free triethyl amine. The dimethyl sulfoxide product solution is thenplaced in a rotary evaporator and most of the dimethyl sulfoxide isremoved by distillation at 15 mm. Hg pressure. The polymer product isdried in a vacuum oven at 15 mm. pressure for 24 hours. Elementalanalyses show values of 60.46% C and 3.38% H which check closely with apolyamide repeating unit structure of the formula:

    --NHC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4

     NHOCC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 CO--                                              (XIIa)

Films of this polymer material show toughness and heat resistance. Otherpolyamides may be made similarly from the above procedure using othercombinations of XI and I compounds, for example:

Ij with XIa

Ij with XIb

Ij with XIc

Ij with XId

Ik with XIf

Ik with XIg

Ik with XIh

Ik with XIi

Ik with XIj

Moreover similar polyamides are made using the XI diamines with thediacids such as Ih and Ii and with the diesters such as Ia through Icwith appropriate modifications in conditions.

EXAMPLE XIII

Preparation of Ketones of the Formula

    R"COArO--A--OArCOR"                                        (XIII)

(wherein R" is a hydrocarbon group of 1-20 carbon atoms)

The procedure of Example I is repeated using in place of the p-hydroxyphenyl benzoate, 1 mole (136 gms.) of p-hydroxy acetophenone. Theproduct recrystallized from alcohol-acetone solution shows elementalanalyses of 66.78% C and 4.18% H agreeing closely with the compound ofthe formula:

    [CH.sub.3 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                                 (XIIIa)

Replacement of the p-hydroxy acetophenone with equivalent amountsrespectively of p-hydroxy-3-methyl-acetophenone,1-hydroxy-6-acetyl-naphthalene, 4-hydroxy-4'-acetyl-diphenyl and4-hydroxy-5'-benzoyl-diphenyl oxide produce the following compoundsrespectively:

    [CH.sub.3 COC.sub.6 H.sub.3 (CH.sub.3)OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                         (XIIIb)

    [CH.sub.3 COC.sub.10 H.sub.6 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                                 (XIIIc)

    [CH.sub.3 COC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                 (XIIId)

    [C.sub.6 H.sub.5 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                        (XIIIe)

When the 4,4'-bis(4-chlorobenzenesulfonyl)diphenyl ether is replacedwith an equivalent amount of 4,4'-bis(4-chlorobenzenesulfonyl)diphenylsulfone in each of the preceding procedures of Example XIII, thefollowing compounds are obtained:

    [CH.sub.3 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                          (XIIIf)

    [CH.sub.3 COC.sub.6 H.sub.3 (CH.sub.3)OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                  (XIIIg)

    [CH.sub.3 COC.sub.10 H.sub.6 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                          (XIIIh)

    [CH.sub.3 COC.sub.6 H.sub.4 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                          (XIIIi)

    [C.sub.6 H.sub.5 COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                 (XIIIj)

The acetyl groups in the above Example XIII products may be converted tothe acetylene-terminated compounds of Example V, namely Vc and Vh. Thesediacetyl compounds, such as XIIIa, b, c, d, f, g, h and i, are reactedwith 2 moles of PCl₅ in 282 gms. (4 moles) of dimethylformamide (DMF)and 80 gms. (2 moles) of NaOH per mole of the diacetyl compound to givethe acetylene-terminated compounds of this invention such as Vc and Vh,which are capable of being polymerized to tough, heat and solventresistant polymers by means of free radical-generating catalysts.

EXAMPLE XIV

Preparation of Tetracarboxylic Derivatives

    (DOOC).sub.2 ArO--A--OAr(COOD).sub.2                       (XIV)

The procedure of Example Ia is repeated using 210.19 gm. (1 mole) of4-hydroxy-dimethylphthalate. Elemental analyses of the recrystallizedproduct gives values of 60.89% C and 3.91% H which correspond closelywith the calculated values for the compound of the formula

    [(CH.sub.3 OOC).sub.2 C.sub.6 H.sub.3 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                         (XIVa)

Repetition of this procedure using (Cl--C₆ H₄ SO₂ C₆ H₄)₂ SO₂ as theX--A--X component yields a product whose elemental analyses of 57.69% Cand 37.40% H check closely with the compound having the formula

    [(CH.sub.3 OOC).sub.2 C.sub.6 H.sub.3 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                  (XIVb)

Corresponding results are obtained using the diethyl, divinyl,dipropargyl, dicyclohexyl esters as starting materials in place of the4-hydroxy-dimethylphthalate, and also when other X--A--X compounds areused in place of those used above.

Hydrolysis of XIVa and XIVb with aqueous NaOH solution produces therespective free acids:

    [(HOOC).sub.2 C.sub.6 H.sub.3 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                                 (XIVa)

and

    [(HOOC).sub.2 C.sub.6 H.sub.3 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                          (XIVb)

Reaction of these free acids with thionyl chloride gives thecorresponding acid chlorides:

    [(ClOOC).sub.2 C.sub.6 H.sub.3 O--C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 O                                                 (XIVc)

and

    [(ClOOC).sub.2 C.sub.6 H.sub.3 O-C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 ].sub.2 SO.sub.2                                          (XIVd)

When these XIV compounds are reacted with NHR₂ amines under amidationconditions, the amides XIVe are prepared. With diamines, the amidationproducts are polymeric polyamides XIVf, whose formula is given above.

EXAMPLE XV

Preparation of Dianhydride of Formula

    O(OC).sub.2 ArO--A--OAr(CO).sub.2 O                        (XV)

One hundreth mole (8.1 gms.) of the tetracid XIVa dissolved in 25 ml ofdimethyl sulfoxide is placed under a nitrogen atmosphere in a 100 mlthree-neck round bottom flask equipped with a magnetic stirrer,thermometer, condenser, gas inlet tube and dropping funnel. Then 4.1gms. (0.04 mole) of acetic anhydride is added and the mixture refluxedfor one hour. Then the apparatus is arranged for distillation anddistillation conducted for essentially complete removal of excess aceticanhydride and by-product acetic acid. The remaining solution containsthe dianhydride having the formula:

    O(OC).sub.2 C.sub.6 H.sub.3 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.3 (CO).sub.2 O (XVa)

Elemental analyses of 61.93% C and 2.80% H check closely with thetheoretical values for this formula. This solution is cooled to roomtemperature and a solution of 1.08 gms. (0.01 mole) ofp-phenylenediamine in 15 ml of dimethylsulfoxide is added gradually overa period of 15 minutes. The reaction, which is exothermic, is maintainedat 40° C. during the addition, and then at 85°-90° C. for 15 minutes.The intermediate at this point has the amic acid repeating unitstructure: ##STR9## To this solution is added 3.06 gm. (0.03 mole) ofacetic anhydride and the mixture is heated at 125° C. for 1.5 hours.Then the solvents are removed in a rotary flash evaporator. The residualsolid is washed with anhydrous ether and dried in a vacuum oven.Elemental analyses values of C:65.12% and H:3.02% are in good agreementwith the calculated values for the polymeric repeating unit structure:

    >NC.sub.6 H.sub.4 N(OC).sub.2 C.sub.6 H.sub.3 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.3 (CO).sub.2 <                                              (XVc)

When the foregoing procedure is repeated using dianhydride compound XIVbin place of XIVa, the resultant polymer has the repeating unit formula:

    >NC.sub.6 H.sub.4 N(OC).sub.2 C.sub.6 H.sub.3 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.3 (CO).sub.2 <                                      (XVd)

for which the elemental analyses of 61.68% C and 2.85% H agree closelywith the calculated values. Films of these polymers are tough and showgood solvent and heat resistance.

When the foregoing procedures are repeated with other dianhydrides ofthis invention and with other diamines, similar polymeric polysulfonepolyimides are obtained.

The various compositions and derivatives described above may berepresented by the formula:

    M--ArSO.sub.2 Ar'QAr'SO.sub.2 Ar--M

wherein Ar, Ar' and Q are as defined above and M represents the variousgroups described above.

When M is monovalent the M--A--M compound is mononomeric, such as, forexample, when M represents the following groups:

    ______________________________________                                        (a)  DOOCArO--     (from formula I)                                           (b)  R.sub.2 NOCArO--                                                                            (from formula II)                                          (c)  KO--          (from formula V) wherein K is an                                              aromatic group having terminal                                                CH.sub.2 ═CH-- or CH.tbd.C--                           (d)  HOArO--       (from formula VI)                                          (e)  NR.sub.2 ArO--                                                                              (from formula XI)                                          (f)  R"C(O)ArO--   (from formula XIII)                                        (g)  (DOOC).sub.2 ArO--                                                                          (from formula XIV)                                         (h)  O(OC).sub.2 ArO--                                                                           (from formula XV)                                          ______________________________________                                    

When M is divalent the M--A--M composition may be polymeric withrepeating units of the following respective formulas:

    __________________________________________________________________________    (i)                                                                              --NR--R'--NR(O)CArO--A--OArC(O)--                                                                        (from formula III) -(j) --OR'O(O)CArO--A--OA                                  rC(O)-- (from formula IV)                       (k)                                                                              --CHRAr"(OH)O--A--OAr"(OH)--                                                                             (from formula VII)                              (l)                                                                              --(O)CArC(O)OArO--A--OArO--                                                                              (from formula VIII)                             (m)                                                                              --(O)COArO--A--OArO--      (from formula IX)                               (n)                                                                              --(O)CArO--A--OArC(O)OArO--A--OArO--                                                                     (from formula X)                                (o)                                                                              --N(R)ArO--A--OArN(R)(O)CArO-- A--OArC(O)--                                                              (from formula XII)                              __________________________________________________________________________

Typical polymeric forms may be represented by the following respectiveformulas which also show terminally attached groups in accordance withthe methods of preparation shown in the respective examples:

    __________________________________________________________________________    (i')                                                                             H--[NHC.sub.6 H.sub.4 NH(O)CC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2         C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6            H.sub.4 C(O)--].sub.n OH                                                      (from Example III)                                                            or in the generic form                                                        H--[NR--R'--NR(O)CArO--A--OArC(O)--].sub.n OH                              (j')                                                                             H--[OCH.sub.2 CH.sub.2 O(O)CC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2         C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6            H.sub.4 C(O)--].sub.n OH                                                      (from Example IV)                                                             or in the generic form                                                        H--[OR'O(O)CArO--A--OCArC(O)--].sub.n OH                                   (k')                                                                             HO--[CH.sub.2 --C.sub.6 H.sub.3 (OH)OC.sub.6 H.sub.4 SO.sub.2 C.sub.6         H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.3            (OH)--].sub.n H                                                               (from Example VII)                                                            or in the generic form                                                        HO[CH(R)Ar"(OH)O--A--OAr"(OH)--].sub.n H                                   (l')                                                                             Cl--[(O)CC.sub.6 H.sub.4 C(O)C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2        C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6            H.sub.4 O--].sub.n H                                                          (from Example VIII)                                                           or in the generic form                                                        Cl--[(O)CArC(O)ArO--A--OArO--].sub.n H                                     (m')                                                                             Cl--[(O)COC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4           OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--].sub.n         H                                                                             (from Example IX)                                                             or in the generic form                                                        Cl--[(O) COArO--A--OArO--].sub.n H                                         (n')                                                                             CH.sub.3 O--[(O)CC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6            H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4            C(O)O--                                                                       --C.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2          C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 O--].sub.n          H                                                                             (from Example X)                                                              or in the generic form                                                        D--[ (O)CArO--A--OArC(O)OArO--A--OArO--].sub.n H                           (o')                                                                             H[--NHC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4               SO.sub.2 C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4            NH--                                                                          (O)CC.sub.6 H.sub.4 OC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 SO.sub.2        C.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OC.sub.6 H.sub.4 C(O)].sub.n         --Cl                                                                          (from Example XII)                                                            or in the generic form                                                        H[--N(R)ArO--A--OArN(R)(O)CArO--A--OArC(O)--].sub.n Cl                     __________________________________________________________________________

In the above formulas, n is an integer having a value of 1-50 or morepreferably 1-20. When n equals 1, the compound is monomeric and when nequals 2 or more, the composition is polymeric. In either case theterminal valencies may be satisfied with various groups such as may beon the starting compounds or derived therefrom such as H, R, RCO, etc.Again the terminal groups will depend on the manner in which therepeating unit structure is recited or divided. For example, in thegeneric formula j' which is given above as

(1) H--[OR'O(O)CArO--A--OCArC(O)--]_(n) OH wherein n is 1-50 or more);

this may be rewritten several times as follows with n' which has a valueof 0-49 or more, preferably 0-19.

(2) HOR'O(O)CArO-A-OCArC(O)[--ORO(O)CArO--A--OCArC(O)--]_(n') OH

(3) HOR'O(O)CArO[--A--OCArC(O)--ORO(O)CArO--]_(n') A--OCArC(O)--OH

(4) HOR'O[(O)CArO--A--OCArC(O)--OR'O]_(n') (O)CArO--A--OCArC(O)--OH

(5) HOR'O(O)CArO--A--[OCArC(O)--OR'O(O)CArO--A--]_(n') OCArC(O)--H

It may be seen therefore that various portions of the respectiveformulas may be taken as the repeating unit.

When n of formula (1) has a value of 1, the compound is monomeric andwhen n' of formulas (2) through (5) has a value of zero, the compound ismonomeric. With higher values of either, the compound is a polymerhaving a plurality of repeating units.

These represent five ways of writing formulas for the same compoundwhereby the arrangement of the repeating unit is given a modifiedsequence and the terminal groups are modified accordingly. In theseformulas the repeating unit as given within the brackets for formulas(2) through (5) may be selected almost arbitrarily thereby causing avariation in the terminal groups at the left and right ends of therespective formulas. While the formula arrangement of (1) is preferred,the various arrangements of (2) through (5) are permissible.

Moreover while the terminal groups are generally in the startingcomponents, it is also possible that during the processing a terminalgroup may be converted to another group. For example, when an acidchloride is a terminal group in a starting component, the activechlorine at one terminal of the long chain may come into contact withwater during processing and be converted to OH. Such reactive groupsalso may subsequently be deliberately converted to other groups, such asesters, by reaction with an alcohol.

It is preferred in the preparation of the above polymers thatapproximately equimolar amounts of the components or reagents should beused. In such cases the terminal group at one end will be derived fromone component and the group at the other end will be derived from theother component. When one component or reagent is used in excess, theresultant polymer generally has both terminal groups derived from thecomponent used in excess. However the use of a component in considerableexcess will cause a limit on the molecular weight of the product andgenerally the more the excess the shorter will be the length of theresulting polymer molecule.

As disclosed above, the compositions of this invention hava a variety ofutilities. For example, compositions of formulas I, II, VI, XI, XIII andXIV are particularly useful for blending with polyethylene terephthalate(PET) and polybutyleneterephthalate (PBT) to upgrade and improve theirproperties and also to improve their crystallization rates. Compositionsof formulas V and XV can be used as intermediates in the formation ofpolymeric products of good properties. The polymeric compositions offormulas III, IV, VII, VIII, IX, X and XII give tough films and coatingsof good heat and solvent resistance and may be molded to give productsof excellent strength and work-loading properties. The polymericcompositions may be cured by heat and pressure with and without variousfillers, modifiers, etc., to give shaped products of excellentproperties.

In Example X, the polymers (b) through (g) have the following respectiverepeating unit formulas:

(b) --(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)-

OC₆ H₄ OC₆ H₄ OC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ OC₆ H₄ O--

(c) --(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)-

OC ₆ H₄ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C₆ H₄ O--

(d) --(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)-

OC₆ H₄ C(CH₃)₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(CH₃)₂ C₆H₄ O--

(e) --(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)-

OC₆ H₄ CH₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ CH₂ C₆ H₄ O--

(f) --(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)-

OC₁₀ H₆ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₁₀ H₆ O--

(g) --(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)-

OC₆ H₄ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C₆ H₄O--

In Example XII various polyamides produced therein have the followingrespective repeating units:

Ij with XIa:

--NC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ij with XIb:

--NHC₆ H₄ OC₆ H₃ (CH₃)SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₃ (CH₃)OC₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ij with XIc:

--NHC₆ H₄ OC₆ H₃ (CH₃)SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₃ (CH₃)OC₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ij with XId:

--NHC₆ H₄ OC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ OC₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ik with XIf:

--NHC₆ H₄ OC₁₀ H₆ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₁₀ H₆ OC₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ik with XIg:

--NHC₆ H₄ OC₆ H₄ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C₆ H₄OC₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ik with XIh:

--NHC₁₀ H₆ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₁₀ H₆ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ik with XIi:

--NHC₆ H₄ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

Ik with XIj:

--NHC₆ H₄ OC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ OC₆ H₄ NH-

(O)CC₆ H₄ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₄ C(O)--

In Example XIV amides XIVe have the following respective formulas:

From XIVa and XIVc:

(R₂ NOC)₂ C₆ H₃ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₄ SO₂ C₆ H₄ OC₆ H₃ (CONR₂)₂

From XIVb and XIVd:

(R₂ NOC)₂ C₆ H₃ OC₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ SO₂ C₆ H₄ OC₆ H₃ (CONR₂)₂

In this same Example XIV polymeric polyamides XIVf have the followingtypical repeating units: ##STR10##

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will of course beapparent that other modifications can be made within the spirit andscope of this invention, and it is not intended to limit the inventionto the exact details insofar as they are defined in the followingclaims.

The invention claimed is:
 1. A polysulfone composition having theformula M--ArSO₂ Ar'QAr'SO₂ Ar--M wherein:Ar and Ar' represent divalentaromatic groups and 2-5 of said divalent aromatic groups linked by O, S,C(O), N(R"), SO₂ or an aliphatic hydrocarbon group: Q is either O orSO₂, and M is a group selected from the class consisting of:(a)DOOCArO-- (b) R₂ NOCArO-- (c) KO-- (d) HOArO-- (e) R"C(O)ArO-- (f)(DOOC)₂ ArO-- (g) O(OC)₂ ArO-- (h)--NR--R'--NR(O)CArO--A--OArC(O)-- (i)--OR'O(O)CArO--A--OArC(O)-- (j) --CHRAr"(OH)O--A--OAr"(OH)-- (k)--(O)CArC(O)OArO--A--OArO-- (l) --(O)COArO--A--OArO-- (m)--(O)CArO--A--OArC(O)OArO--A--OArO-- (n)--N(R)ArO--A--OArN(R)(O)CAr--A--ArC(O)--wherein Ar is as defined above:D represents hydrogen, halogen or a monovalent hydrocarbon group of oneto 20 carbon atoms; R is a hydrogen or a hydrocarbon group or 2-5 ofhydrocarbon groups joined by --O--, --S--, --COO--, --OOC-- or --SO₂ --;R' is a divalent hydrocarbon group; R" is a hydrocarbon group of 1-20carbon atoms; K is an aromatic group having a terminal vinyl oracetylene radical; Ar" is a trivalent aromatic group; and A representsthe divalent radical --ArSO₂ Ar'QAr'SO₂ Ar--.
 2. The composition ofclaim 1, having the formula DOOCArO--ArSO₂ Ar'QAr'SO₂ ArCOOD, wherein D,Ar and Q are as defined in claim
 1. 3. The composition of claim 2,having the formula ROOCArO-ArSO₂ Ar'QAr'SO₂ ArCOOR, wherein D, Ar, Q andR are as defined in claim
 1. 4. The composition of claim 2, in which Ris CH₃.
 5. The composition of claim 2, in which R is C₆ H₅.
 6. Thecomposition of claim 4 in which Q is O.
 7. The composition of claim 5 inwhich Q is O.
 8. The composition of claim 4 in which Q is SO₂.
 9. Thecomposition of claim 5 in which Q is SO₂.
 10. The composition of claim2, in which D is H.
 11. The composition of claim 10, in which Q is O.12. The composition of claim 10, in which Q is SO₂.
 13. The compositionof claim 2, in which D is Cl.
 14. The composition of claim 13, in whichQ is O.
 15. The composition of claim 13, in which Q is SO₂.
 16. Thecomposition of claim 1 having the formula R₂ N(O)CArO--ArSO₂ Ar'QAr'SO₂Ar--OArC(O)NR₂ wherein R, Ar' and Q are as defined in claim
 1. 17. Thecomposition of claim 1 which has the formula H₂ N(O)CArO--ArSO₂Ar'QAr'SO₂ Ar--OArC(O)NH₂ wherein Ar, Ar' and Q are as defined inclaim
 1. 18. The composition of claim 1 which has the formula KO--ArSO₂Ar'QAr'SO₂ Ar--OK wherein K, Ar, Ar' and Q are as defined in claim 1.19. The composition of claim 1 which has the formula HOArO--ArSO₂Ar'QAr'SO₂ Ar--O--ArOH, wherein K, Ar, Ar' and Q are as defined inclaim
 1. 20. The composition of claim 1 which has the formula NR₂ArO--ArSO₂ Ar'SO₂ Ar'SO₂ Ar--OArNR₂, wherein R, Ar and Ar' are asdefined in claim
 1. 21. The composition of claim 1 which has the formulaR"C(O)ArO--ArSO₂ Ar'QAr'SO₂ Ar--OArC(O)R", wherein R", Ar, Ar' and Q areas defined in claim
 1. 22. The composition of claim 1 which has theformula (DOOC)₂ ArO--ArSO₂ Ar'QAr'SO₂ Ar--OAr(COOD)₂ wherein D, Ar, Ar'and Q are as defined in claim
 1. 23. The composition of claim 1 whichhas the formula O(OC)₂ ArO--ArSO₂ Ar'QAr'SO₂ Ar--OAr(CO)₂ O wherein Ar,Ar' and Q are as defined in claim
 1. 24. The composition of claim 1which has the formula [--N(R)-R'--N(R)(O)CArOArSO₂ Ar'QAr'SO₂ArOArC(O)--]_(n) wherein n is an integer having a value of 1-50, and R,R', Ar, Ar' and Q are as defined in claim
 1. 25. The composition ofclaim 1 which has the formula [--OR'O(O)CArO--ArSO₂ Ar'QAr'SO₂ArOArC(O)--]_(n) wherein n is an integer having a value of 1-50, and R',Ar, Ar' and Q are as defined in claim
 1. 26. The composition of claim 1which has the formula [--CH(R)Ar"(OH)O--ArSO₂ Ar'QArSO₂Ar--OAr"(OH)--]_(n) wherein n is an integer having a value of 1-50 andR, Ar, Ar', Ar" and Q are as defined in claim
 1. 27. The composition ofclaim 1 which has the formula [--(O)CArC(O)OArO--ArSO₂ Ar'QAr'SO₂Ar--OArO--]_(n) wherein n is an integer having a value of 1-50 and Ar,Ar' and Q are as defined in claim
 1. 28. The composition of claim 1which has the formula [--(O)COArO--ArSO₂ Ar'QAr'SO₂ Ar--OArO--]_(n)wherein n is an integer having a value of 1-50 and Ar, Ar' and Q are asdefined in claim
 1. 29. The composition of claim 1 which has the formula[--(O)CArO--ArSO₂ Ar'QAr'SO₂ Ar--OArC(O)OArO--ArSO₂ Ar'QAr'SO₂Ar--OArO--]_(n) wherein n is an integer having a value of 1-50 and Ar,Ar' and Q are as defined in claim
 1. 30. The composition of claim 1which has the formula [--N(R)ArO--ArSO₂ Ar'QAr'SO₂Ar--OArN(R)(O)CAr--]_(n) wherein n is an integer having a value of 1-50and R, Ar, Ar' and Q are as defined in claim 1.